JP2001246256A - Catalyst for hydrogenation reaction of carbon monoxide and method for preparing hydrogenated product - Google Patents
Catalyst for hydrogenation reaction of carbon monoxide and method for preparing hydrogenated productInfo
- Publication number
- JP2001246256A JP2001246256A JP2000064874A JP2000064874A JP2001246256A JP 2001246256 A JP2001246256 A JP 2001246256A JP 2000064874 A JP2000064874 A JP 2000064874A JP 2000064874 A JP2000064874 A JP 2000064874A JP 2001246256 A JP2001246256 A JP 2001246256A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- transition metal
- carbon monoxide
- porous body
- fuel oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 19
- 239000011148 porous material Substances 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 33
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 claims abstract description 31
- 239000000295 fuel oil Substances 0.000 claims abstract description 23
- 239000003502 gasoline Substances 0.000 claims abstract description 23
- 239000002283 diesel fuel Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 101150076749 C10L gene Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 102200118166 rs16951438 Human genes 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、一酸化炭素の水素
化反応触媒および主にガソリン燃料油およびディーゼル
燃料油を含む水素化生成物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for hydrogenating carbon monoxide and a method for producing a hydrogenation product mainly containing gasoline fuel oil and diesel fuel oil.
【０００２】[0002]
【従来の技術】一酸化炭素と水素の混合ガス（合成ガ
ス）から製造される燃料油は、石油から精製される燃料
油のような硫黄酸化物の原因になる硫黄や、すすの発生
源で発ガン性を示す芳香族炭化水素（アロマ）を全く含
まないため、石油系燃料に代わる環境低負荷型高品位燃
料として注目されている。2. Description of the Related Art Fuel oil produced from a mixed gas of carbon monoxide and hydrogen (synthesis gas) is a source of sulfur or soot that causes sulfur oxides such as fuel oil refined from petroleum. Because it does not contain any aromatic hydrocarbons (aromatics) that exhibit carcinogenicity, it has attracted attention as an environmentally-friendly, high-grade fuel that replaces petroleum fuels.
【０００３】従来よりシリカ、アルミナの単体にコバル
トやルテニウムを担持させた触媒の存在下で前記合成ガ
スを所定の温度、圧力の下で反応させて前記燃料油成分
を含む水素化生成物を製造することが行われている。し
かしながら、これらの方法では目的とする成分（例えば
ガソリン燃料油成分またはディーゼル燃料油成分）を他
の成分（メタン等）に比べて高い選択率で製造するとい
う点で必ずしも十分満足するものではなかった。Conventionally, the synthesis gas is reacted at a predetermined temperature and pressure in the presence of a catalyst in which cobalt or ruthenium is supported on a simple substance of silica or alumina to produce a hydrogenated product containing the fuel oil component. That is being done. However, these methods are not always satisfactory in that a target component (for example, a gasoline fuel oil component or a diesel fuel oil component) is produced with a higher selectivity than other components (such as methane). .
【０００４】[0004]
【発明が解決しようとする課題】本発明は、水素と一酸
化炭素の混合ガスから目的とする成分（例えばガソリン
燃料油成分またはディーゼル燃料油成分）を高い選択率
で含む水素化生成物を製造するのに適した一酸化炭素の
水素化反応触媒を提供するものである。SUMMARY OF THE INVENTION The present invention provides a method for producing a hydrogenation product containing a target component (for example, a gasoline fuel oil component or a diesel fuel oil component) at a high selectivity from a mixed gas of hydrogen and carbon monoxide. It is intended to provide a catalyst for hydrogenating carbon monoxide suitable for the reaction.
【０００５】本発明は、水素と一酸化炭素の混合ガスか
ら目的とする成分（例えばガソリン燃料油成分またはデ
ィーゼル燃料油成分）が高い選択率で含む水素化生成物
を製造することが可能な方法を提供するものである。The present invention provides a method for producing a hydrogenation product containing a target component (eg, a gasoline fuel oil component or a diesel fuel oil component) at a high selectivity from a mixed gas of hydrogen and carbon monoxide. Is provided.
【０００６】[0006]
【課題を解決するための手段】本発明に係る一酸化炭素
の水素化反応触媒は、全細孔の９０％以上が直径１〜５
０ｎｍの微細孔を有する多孔体に遷移金属を担持したこ
とを特徴とするものである。According to the catalyst for hydrogenating carbon monoxide according to the present invention, 90% or more of all the pores have a diameter of 1-5.
The transition metal is supported on a porous body having fine pores of 0 nm.
【０００７】本発明に係る水素化生成物の製造方法は、
全細孔の９０％以上が直径１〜５０ｎｍの微細孔を有す
る多孔体に遷移金属を担持した触媒の存在下、水素と一
酸化炭素を含む混合ガスを２００〜４００℃の温度、
０．１〜１０ＭＰａの圧力の下にて反応させることを特
徴とするものである。[0007] The method for producing a hydrogenation product according to the present invention comprises:
In the presence of a catalyst in which 90% or more of all the pores have a transition metal supported on a porous body having fine pores having a diameter of 1 to 50 nm, a mixed gas containing hydrogen and carbon monoxide is heated at a temperature of 200 to 400 ° C.
The reaction is performed under a pressure of 0.1 to 10 MPa.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【０００９】本発明に係る一酸化炭素の水素化反応触媒
は、全細孔の９０％以上が直径１〜５０ｎｍの微細孔を
有する多孔体に遷移金属または貴金属を担持した構成を
有する。The catalyst for hydrogenating carbon monoxide according to the present invention has a structure in which a transition metal or a noble metal is supported on a porous body having 90% or more of all the pores having fine pores having a diameter of 1 to 50 nm.
【００１０】前記多孔体は、例えば純粋なシリカ、また
はこの純粋なシリカをベースとし、アルミニウムやガリ
ウムのような金属を導入したものからなる。The porous body is made of, for example, pure silica or a material based on the pure silica, into which a metal such as aluminum or gallium is introduced.
【００１１】ここで、『細孔直径』とは細孔直径の分布
を測定し、そのピークトップを細孔直径とした。Here, the term "pore diameter" refers to the measurement of the distribution of the pore diameter, and the peak top is defined as the pore diameter.
【００１２】前記多孔体の微細孔の寸法および微細孔分
布を前記範囲に規定することにより遷移金属を微細な状
態で、かつ均一に分散した状態で担持することが可能に
なる。前記多孔体は、直径１〜１０ｎｍの微細孔が全細
孔の９０％以上を占めることがより好ましい。このよう
なシリカ多孔体は、例えばモービル社が開発したＭＣＭ
−４１，東京大学および豊田中央研究所が開発したＦＳ
Ｍ−１６またはスタンホード大学が開発したＳＢＡ−１
５が知られている。ＭＣＭ−４１は、シリカ源および界
面活性剤（テンプレート；鋳型）としてそれぞれケイ酸
ナトリウムおよびヘキサデシルトリメチルアンモニウム
を用い、これらを加圧反応器（オートクレーブ）中、１
２０℃にて水熱合成することにより製造される。By defining the size and distribution of the fine pores of the porous body within the above ranges, the transition metal can be supported in a fine state and in a uniformly dispersed state. More preferably, in the porous body, micropores having a diameter of 1 to 10 nm occupy 90% or more of all the pores. Such a porous silica material is, for example, an MCM developed by Mobile.
-41, FS developed by the University of Tokyo and Toyota Central Research Institute
M-16 or SBA-1 developed by Stanford University
5 are known. MCM-41 uses sodium silicate and hexadecyltrimethylammonium as a silica source and a surfactant (template; template), respectively, and these are placed in a pressure reactor (autoclave) for 1 hour.
It is produced by hydrothermal synthesis at 20 ° C.
【００１３】前記遷移金属としては、例えばコバルト、
ニッケル、鉄、銅、クロム、マンガン、ジルコニア、モ
リブデン、タングステン、レニウム、オスミウム、イリ
ジウム、パラジウム、銀、ルテニウム、ロジウム、金、
白金等を用いることができる。特に、コバルト、鉄、ル
テニウム、ロジウム、白金が好ましい。As the transition metal, for example, cobalt,
Nickel, iron, copper, chromium, manganese, zirconia, molybdenum, tungsten, rhenium, osmium, iridium, palladium, silver, ruthenium, rhodium, gold,
Platinum or the like can be used. Particularly, cobalt, iron, ruthenium, rhodium and platinum are preferred.
【００１４】前記遷移金属は、コバルトまたは鉄である
場合、前記多孔体に５〜４０重量％の範囲で担持され、
ルテニウム、ロジウムまたは白金から選ばれる貴金属で
ある場合、前記多孔体に１〜１５重量％の範囲で担持さ
れることが好ましい。前記遷移金属の担持量が前記範囲
の下限値未満にすると、後述する水素と一酸化炭素の混
合ガスの反応時における一酸化炭素の転化率が低下する
虞がある。一方、前記遷移金属の担持量が前記範囲の上
限値を超えてもそれに見合った一酸化炭素の転化率の向
上が期待できない。When the transition metal is cobalt or iron, the transition metal is supported on the porous body in a range of 5 to 40% by weight,
In the case of a noble metal selected from ruthenium, rhodium or platinum, it is preferably supported on the porous body in a range of 1 to 15% by weight. If the amount of the supported transition metal is less than the lower limit of the range, the conversion rate of carbon monoxide during the reaction of a mixed gas of hydrogen and carbon monoxide, which will be described later, may decrease. On the other hand, even if the amount of the supported transition metal exceeds the upper limit of the above range, a corresponding increase in the conversion of carbon monoxide cannot be expected.
【００１５】前述した一酸化炭素の水素化反応触媒は、
例えば次のようなＩＭＰ法またはＴＩＥ法により製造さ
れる。The above-mentioned catalyst for hydrogenating carbon monoxide comprises:
For example, it is manufactured by the following IMP method or TIE method.
【００１６】（ＩＭＰ法）まず、例えばモービル社が開
発したＭＣＭ−４１のような多孔体を空気焼成して残留
する界面活性剤（テンプレート）を５００〜６００℃の
温度で燃焼、除去する。つづいて、焼成した多孔体を遷
移金属化合物の水溶液に浸漬してその水溶液を前記多孔
体に含浸する。その後乾燥し、再度、５００〜６００℃
の温度で焼成して目的とする触媒を製造する。(IMP method) First, a porous material such as MCM-41 developed by Mobile Co., Ltd. is fired in air, and the remaining surfactant (template) is burned and removed at a temperature of 500 to 600 ° C. Subsequently, the fired porous body is immersed in an aqueous solution of a transition metal compound to impregnate the porous body with the aqueous solution. Thereafter, it is dried and again at 500 to 600 ° C.
To produce the desired catalyst.
【００１７】（ＴＩＥ法）まず、例えばモービル社が開
発したＭＣＭ−４１のような多孔体を遷移金属化合物の
水溶液に添加、混合する。この時、多孔体には界面活性
剤（テンプレート）が残留するため、遷移金属イオンと
テンプレートイオンとが交換される。つづいて、この混
合物を乾燥した後、５００〜６００℃の温度で焼成して
前記テンプレートを燃焼、除去することにより目的とす
る触媒を製造する。(TIE method) First, a porous material such as MCM-41 developed by Mobil is added to and mixed with an aqueous solution of a transition metal compound. At this time, since the surfactant (template) remains in the porous body, transition metal ions and template ions are exchanged. Subsequently, after drying this mixture, it is calcined at a temperature of 500 to 600 ° C. to burn and remove the template to produce a target catalyst.
【００１８】前記各製造方法において、ＴＩＥ法で作ら
れた触媒は遷移金属を担持する工程で多孔体の細孔が潰
れず、一定の範囲の細孔が規則正しく配列されている、
つまり遷移金属を担持する前の多孔体の細孔構造を保っ
たまま多量の遷移金属を担持することができるため好ま
しい。In each of the above-mentioned production methods, the catalyst produced by the TIE method does not collapse the pores of the porous body in the step of supporting the transition metal, and the pores in a certain range are regularly arranged.
That is, a large amount of transition metal can be supported while maintaining the pore structure of the porous body before supporting the transition metal, which is preferable.
【００１９】次に、本発明に係る水素化生成物の製造方
法を説明する。Next, a method for producing a hydrogenation product according to the present invention will be described.
【００２０】前述した全細孔の９０％以上が直径１〜５
０ｎｍの微細孔を有する多孔体に遷移金属を担持した触
媒の存在下、水素と一酸化炭素を含む混合ガスを２００
〜４００℃の温度、０．１〜１０ＭＰａの圧力の下にて
反応させることによりガソリン燃料油成分、ディーゼル
燃料成分を含む水素化生成物を製造する。At least 90% of all the pores mentioned above have a diameter of 1 to 5
In the presence of a catalyst in which a transition metal is supported on a porous body having fine pores of 0 nm, a mixed gas containing hydrogen and carbon monoxide was added to a mixture of 200 μm
A hydrogenated product containing a gasoline fuel oil component and a diesel fuel component is produced by reacting at a temperature of ４００400 ° C. under a pressure of 0.1 to 10 MPa.
【００２１】具体的には、円筒状のステンレス製高圧反
応管内に例えば粉末状の前記触媒を充填し、この反応管
を例えば外部に配置したヒータでその内部温度が２００
〜４００℃になるように加熱した状態で、水素と一酸化
炭素を含む高圧混合ガス（０．１〜１０ＭＰａ）を流通
させることにより水素化生成物を製造する。More specifically, a cylindrical stainless steel high-pressure reaction tube is filled with, for example, the above-mentioned powdered catalyst, and the reaction tube is arranged, for example, with a heater arranged outside to have an internal temperature of 200 mm.
A hydrogenated product is produced by flowing a high-pressure mixed gas (0.1 to 10 MPa) containing hydrogen and carbon monoxide in a state where the mixture is heated to about 400 ° C.
【００２２】この他に、出入口を有する高圧タンク内に
高沸点有機溶媒に粉末状の前記触媒を分散させたスラリ
ーを入れ、この高圧タンクを例えば外部に配置したヒー
タでその内部温度が２００〜４００℃になるように加熱
した状態で、水素と一酸化炭素を含む高圧混合ガス
（０．１〜１０ＭＰａ）を前記入口から前記スラリー内
に流通させることにより水素化生成物を製造することも
可能である。In addition, a slurry in which the powdered catalyst is dispersed in a high-boiling organic solvent is placed in a high-pressure tank having an inlet / outlet. It is also possible to produce a hydrogenated product by flowing a high-pressure mixed gas (0.1 to 10 MPa) containing hydrogen and carbon monoxide from the inlet into the slurry in a state where the mixture is heated to a temperature of 0 ° C. is there.
【００２３】前記触媒は、粉末状（例えば平均粒径５０
〜１５０μｍ）の他に、この粉末を成型してペレットと
したものを粉砕した顆粒状の形態でも使用することがで
きる。The catalyst is in the form of a powder (for example, having an average particle size of 50
In addition to this, the powder can be used in the form of granules obtained by molding the powder into pellets and then pulverizing the pellets.
【００２４】前記混合ガスの各成分比率は、水素化生成
物中に選択される目的とする成分の種類等に依存するた
め、一概に規定できないが、通常、水素（Ｈ2）：一酸
化炭素（ＣＯ）＝１：１〜４：１にすることが好まし
い。例えば、選択する成分がディーゼル燃料油成分であ
る場合には前記混合ガスとして水素（Ｈ2）：一酸化炭
素（ＣＯ）＝２：１の混合比率のものを用いることが好
ましい。The ratio of each component of the mixed gas depends on the kind of the target component selected in the hydrogenated product and cannot be unconditionally specified, but is usually hydrogen (H 2 ): carbon monoxide. It is preferable that (CO) = 1: 1 to 4: 1. For example, when the component to be selected is a diesel fuel oil component, it is preferable to use a mixed gas of hydrogen (H 2 ): carbon monoxide (CO) = 2: 1 as the mixed gas.
【００２５】前記触媒の存在下で前記混合ガスを反応さ
せる反応系において、温度および圧力を前記範囲に設定
することにより、目的とする成分としてＣ1のメタンか
らＣ4のブタンと、Ｃ5〜Ｃ9のガソリン燃料油成分およ
びＣ10〜Ｃ20のディーゼル燃料油成分と、ワックスのよ
うな高沸点パラフィンとを任意に選択することが可能に
なる。In a reaction system in which the mixed gas is reacted in the presence of the catalyst, by setting the temperature and the pressure within the above ranges, C 1 methane to C 4 butane and C 5 to It is possible to arbitrarily select a gasoline fuel oil component of C 9 and a diesel fuel oil component of C 10 to C 20 and a high-boiling paraffin such as wax.
【００２６】前記混合ガスを前記高圧反応管に供給する
時の流速は、一酸化炭素の転化率に影響を及ぼす。一般
に、前記混合ガスの流速を遅くすると、一酸化炭素の転
化率が高くなるものの、製造された水素化生成物の各成
分の分布も変化して目的とする成分の収量も変化する。
このため、前記混合ガスの流速は目的とする成分の収量
を高める、つまり選択性を高める観点から、０．１ＭＰ
ａ、２０℃換算で、５０〜１００ｃｍ3／分にすること
が好ましい。The flow rate when the mixed gas is supplied to the high-pressure reaction tube affects the conversion of carbon monoxide. In general, when the flow rate of the mixed gas is reduced, the conversion of carbon monoxide increases, but the distribution of each component of the produced hydrogenation product also changes, and the yield of the target component also changes.
For this reason, from the viewpoint of increasing the yield of the target component, that is, increasing the selectivity, the flow rate of the mixed gas is 0.1 MPa.
a, It is preferably 50 to 100 cm 3 / min in terms of 20 ° C.
【００２７】以上説明したように本発明に係る一酸化炭
素の水素化反応触媒は、全細孔の９０％以上が直径１〜
５０ｎｍの微細孔を有する多孔体に遷移金属を担持した
構成を有する。As described above, in the carbon monoxide hydrogenation reaction catalyst according to the present invention, 90% or more of all the pores have a diameter of 1 to 1.
It has a configuration in which a transition metal is supported on a porous body having fine pores of 50 nm.
【００２８】このような構成の触媒は、遷移金属が担持
される多孔体の細孔が極めて微細で、かつその細孔分布
が極めて狭いために、水素と一酸化炭素の混合ガスから
目的とする成分（例えばガソリン燃料油成分またはディ
ーゼル燃料油成分）を高い選択率で含む水素化生成物を
製造するのに適する。In the catalyst having such a structure, the pores of the porous body supporting the transition metal are extremely fine and the pore distribution is extremely narrow. Suitable for producing a hydrogenation product containing a component (eg, a gasoline fuel oil component or a diesel fuel oil component) with high selectivity.
【００２９】特に、前述したＴＩＥ法により作られた触
媒は遷移金属を担持する前の多孔体の細孔構造を保った
まま多量の遷移金属を担持することができるため、目的
とする成分（例えばガソリン燃料油成分またはディーゼ
ル燃料油成分）をより一層高い選択率で含む水素化生成
物の製造に適する。In particular, since the catalyst prepared by the above-described TIE method can support a large amount of transition metal while maintaining the porous structure of the porous body before supporting the transition metal, the target component (for example, It is suitable for the production of hydrogenated products containing a higher selectivity (gasoline fuel component or diesel fuel component).
【００３０】また、遷移金属の担持量を規定（コバルト
の場合、５〜４０重量％、ルテニウムの場合１〜１５重
量％）することによって、水素と一酸化炭素の混合ガス
の反応時における一酸化炭素の転化率を向上できるとと
もに、目的とする成分（例えばガソリン燃料油成分また
はディーゼル燃料油成分）をより一層高い選択率で含む
水素化生成物の製造が可能になる。By regulating the amount of the supported transition metal (5 to 40% by weight in the case of cobalt and 1 to 15% by weight in the case of ruthenium), the amount of monoxide during the reaction of the mixed gas of hydrogen and carbon monoxide is increased. The conversion of carbon can be improved, and the production of a hydrogenated product containing a target component (for example, a gasoline fuel oil component or a diesel fuel oil component) at a higher selectivity becomes possible.
【００３１】さらに、本発明に係る水素化生成物の製造
方法は、前述した触媒の存在下、水素と一酸化炭素を含
む混合ガスを２００〜４００℃の温度、０．１〜１０Ｍ
Ｐａの圧力の下にて反応させるものである。Further, in the method for producing a hydrogenated product according to the present invention, a mixed gas containing hydrogen and carbon monoxide is heated to a temperature of 200 to 400 ° C. and 0.1 to 10 M in the presence of the above-mentioned catalyst.
The reaction is performed under a pressure of Pa.
【００３２】このような方法によれば、細孔が極めて微
細で、かつその細孔分布が極めて狭い多孔体に遷移金属
を担持した触媒を用いるために、この触媒の多数かつ微
細な細孔に存在する遷移金属の活性作用により水素と一
酸化炭素を含む混合ガスから目的とする成分、特にＣ5
〜Ｃ9のガソリン燃料油成分およびＣ10〜Ｃ20のディー
ゼル燃料油成分までの反応が容易に進行してそれら成分
を多く含む水素化生成物を製造することができる。According to such a method, since a catalyst in which a transition metal is supported on a porous body having extremely fine pores and an extremely narrow pore distribution is used, a large number of fine pores of the catalyst are used. The target component, especially C 5 , is produced from the mixed gas containing hydrogen and carbon monoxide by the action of the existing transition metal.
The reaction to the diesel fuel oil component of the gasoline fuel oil component and C 10 -C 20 of -C 9 easily proceeds can be produced hydrogenation product containing a large amount of components thereof.
【００３３】とりわけ、ＴＩＥ法により作られた、遷移
金属を担持する前の多孔体の細孔構造を保ったまま多量
の遷移金属を担持した触媒を用いて前記混合ガスを所定
の温度、圧力の下で反応させることによって、目的とす
る成分（例えばガソリン燃料油成分またはディーゼル燃
料油成分）をより一層高い選択率で含む水素化生成物を
製造することができる。これは、例えば次のような挙動
によるものである。In particular, the mixed gas is heated to a predetermined temperature and pressure using a catalyst prepared by the TIE method and supporting a large amount of transition metal while maintaining the pore structure of the porous body before supporting the transition metal. By reacting below, it is possible to produce a hydrogenation product containing a target component (for example, a gasoline fuel oil component or a diesel fuel oil component) with higher selectivity. This is due to, for example, the following behavior.
【００３４】水素と一酸化炭素の反応時における水素化
生成物の選択性は、炭素連鎖成長確率に依存する。前記
ＴＩＥ法により作られた触媒は、担持される遷移金属の
活性点が細孔の内部に存在するため、前記混合ガスの反
応は主にこの細孔内で進行する。このため、前記混合ガ
スの反応により生成された中間生成物の活性点への再付
着が高くなるため、前記炭素連鎖成長確率が効率よく進
行する。その結果、炭素数が多いＣ5〜Ｃ9のガソリン燃
料油成分およびＣ10〜Ｃ20のディーゼル燃料油成分をよ
り一層高い選択率で含む水素化生成物を製造することが
可能になる。The selectivity of the hydrogenated product during the reaction between hydrogen and carbon monoxide depends on the carbon chain growth probability. In the catalyst produced by the TIE method, the active site of the transition metal to be supported exists inside the pores, so that the reaction of the mixed gas mainly proceeds in the pores. For this reason, since the re-attachment of the intermediate product generated by the reaction of the mixed gas to the active site increases, the carbon chain growth probability proceeds efficiently. As a result, it is possible to produce a hydrogenated product comprising a diesel fuel oil component of the gasoline fuel oil component and C 10 -C 20 in C 5 -C 9 a large number of carbon atoms in even higher selectivity.
【００３５】[0035]
【実施例】以下、好ましい実施例を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments will be described below in detail.
【００３６】（実施例１）まず、全細孔の９１％が直径
１〜９ｎｍの微細孔を有するシリカ多孔体を５５０℃の
温度で焼成して前記シリカ多孔体中の残留界面活性剤
（テンプレート）を燃焼、除去した。つづいて、この多
孔体を５重量％濃度の硝酸コバルト水溶液に浸漬してそ
の水溶液を前記多孔体に含浸した後、再度、５５０℃の
温度で焼成する、ＩＭＰ法によりコバルトが１０重量％
担持された平均粒径７５μｍの粉末状触媒を製造した。Example 1 First, a porous silica having 91% of all pores having fine pores having a diameter of 1 to 9 nm was fired at a temperature of 550 ° C. to obtain a residual surfactant (template) in the porous silica. ) Was burned and removed. Subsequently, the porous body is immersed in a 5% by weight aqueous solution of cobalt nitrate to impregnate the porous body with the aqueous solution, and then calcined again at a temperature of 550 ° C.
A supported powdery catalyst having an average particle size of 75 μm was produced.
【００３７】次いで、得られた粉末状触媒を円筒状のス
テンレス製高圧反応管内に充填し、この反応管を例えば
外部に配置したヒータでその内部温度が２５０℃になる
ように加熱した状態で、水素と一酸化炭素の高圧混合ガ
ス（圧力；２．０ＭＰａ、Ｈ 2：ＣＯ＝２：１）を５０
ｃｍ3／分の流速で流通させることにより水素化生成物
を製造した。Next, the obtained powdery catalyst is placed in a cylindrical
Filled into a Tenres high-pressure reaction tube, this reaction tube
The temperature inside becomes 250 ° C with the heater arranged outside
High-pressure gas mixture of hydrogen and carbon monoxide
(Pressure: 2.0 MPa, H Two: CO = 2: 1) to 50
cmThreeHydrogenation products by flowing at a flow rate of
Was manufactured.
【００３８】（実施例２）まず、全細孔の９１％が直径
１〜９ｎｍの微細孔を有するシリカ多孔体を５重量％濃
度の硝酸コバルト水溶液に添加、混合して、前記シリカ
多孔体中の残留界面活性剤（テンプレート）をＣｏイオ
ンと交換した。つづいて、この混合物を乾燥した後、５
５０℃の温度で焼成して前記テンプレートを燃焼、除去
する、ＴＩＥ法により平均粒径７５μｍの粉末状触媒を
製造した。この触媒は、コバルト担持量が１０重量％
で、かつシリカ多孔体がコバルトを担持する前の微細構
造を保持していた。Example 2 First, a porous silica having 91% of all the pores having fine pores having a diameter of 1 to 9 nm was added to a 5% by weight aqueous solution of cobalt nitrate and mixed. Was replaced with Co ions. Subsequently, after drying this mixture, 5
A powdery catalyst having an average particle diameter of 75 μm was produced by a TIE method in which the template was burned at a temperature of 50 ° C. to burn and remove the template. This catalyst has a cobalt loading of 10% by weight.
And the microstructure before the porous silica supported cobalt.
【００３９】次いで、得られた粉末状触媒を用いて実施
例１と同様な方法により水素化生成物を製造した。Next, a hydrogenated product was produced in the same manner as in Example 1 using the obtained powdery catalyst.
【００４０】（実施例３）ＴＩＥ法により全細孔の９１
％が直径１〜９ｎｍの微細孔を有するシリカ多孔体にＣ
ｏを２０重量％担持した構成を有する触媒を用いた以
外、実施例１と同様な方法により水素化生成物を製造し
た。Example 3 The total pore size of 91 was measured by the TIE method.
% To the porous silica having fine pores having a diameter of 1 to 9 nm.
A hydrogenated product was produced in the same manner as in Example 1, except that a catalyst having a structure supporting 20% by weight of o was used.
【００４１】実施例１〜３で得られた水素化生成物の混
合ガス中の一酸化炭素（ＣＯ）に対する転化率、水素化
生成物の成分を調べた。その結果を下記表１に示す。な
お、成分分析はＣ1のメタンからＣ4のブタンについては
高速ガスクロマトグラフ（ヒューレット・パッカド社製
商品名；Ｍ２００）を用い、Ｃ5以上の液状成分につい
てはガスクロマトグラフ質量分析装置（パーキンエルマ
ー社製商品名；TurboMass）を用いて行った。The conversion ratio of the hydrogenated products obtained in Examples 1 to 3 to carbon monoxide (CO) in the mixed gas and the components of the hydrogenated products were examined. The results are shown in Table 1 below. Incidentally, component analysis fast gas chromatograph (Hewlett-Pakkado trade name; M200) for butane C 4 from methane C 1 using a gas chromatograph mass spectrometer for C 5 or more liquid components (Perkin Elmer (Trade name: TurboMass).
【００４２】[0042]
【表１】 [Table 1]
【００４３】前記表１から明らかなように実施例１〜３
によればＣ5〜Ｃ9のガソリン燃料油成分およびＣ10〜Ｃ
20のディーゼル燃料油成分を比較的高い選択率で含有す
る水素化生成物を製造できることがわかる。As is apparent from Table 1, Examples 1 to 3 were used.
Gasoline fuel oil component and C 10 of the C 5 -C 9 According -C
It can be seen that a hydrogenation product containing 20 diesel fuel components with relatively high selectivity can be produced.
【００４４】特に、ＴＩＥ法によりコバルトを担持した
触媒を用いた実施例２，３ではＣ5〜Ｃ9のガソリン燃料
油成分およびＣ10〜Ｃ20のディーゼル燃料油成分をより
一層高い選択率で含有する水素化生成物を製造できるこ
とがわかる。また、ＴＩＥ法によりコバルトの担持量が
２０重量％の触媒を用いた実施例３ではＣＯ転化率が高
く、かつＣ5〜Ｃ9のガソリン燃料油成分およびＣ10〜Ｃ
20のディーゼル燃料油成分をさらに一層高い選択率で含
有する水素化生成物を製造できることがわかる。[0044] Particularly, in even higher selectivity to diesel fuel oil component of the gasoline fuel oil component of C 5 -C 9 In Examples 2 and 3 using a catalyst carrying cobalt and C 10 -C 20 by TIE method It can be seen that a hydrogenation product containing can be produced. The supported amount of cobalt higher Example 3 In CO conversion with 20 wt% of the catalyst by TIE method, and C 5 gasoline fuel oil component of -C 9 and C 10 -C
It can be seen that a hydrogenated product containing 20 diesel fuel oil components with even higher selectivity can be produced.
【００４５】（実施例４）まず、全細孔の９４％が直径
１〜８ｎｍの微細孔を有するシリカ多孔体を１０重量％
濃度の硝酸ルテニウム水溶液に添加、混合して、前記シ
リカ多孔体中の残留界面活性剤（テンプレート）をＲｕ
イオンと交換した。つづいて、この混合物を乾燥した
後、５５０℃の温度で焼成して前記テンプレートを燃
焼、除去する、ＴＩＥ法により平均粒径５０μｍの粉末
状触媒を製造した。この触媒は、ルテニウム担持量が１
０重量％で、かつシリカ多孔体がコバルトを担持する前
の微細構造を保持していた。Example 4 First, 10% by weight of a silica porous material having 94% of all the pores having fine pores having a diameter of 1 to 8 nm was prepared.
And mixed with a ruthenium nitrate aqueous solution having a concentration of Ru to remove residual surfactant (template) in the porous silica.
Exchanged for ions. Subsequently, the mixture was dried and then calcined at a temperature of 550 ° C. to burn and remove the template, thereby producing a powdery catalyst having an average particle diameter of 50 μm by the TIE method. This catalyst has a ruthenium loading of 1
At 0 wt%, the microstructure before the porous silica supported cobalt was retained.
【００４６】次いで、得られた粉末状触媒を用いて実施
例１と同様に円筒状のステンレス製高圧反応管内に充填
し、この反応管を例えば外部に配置したヒータでその内
部温度が２５０℃になるように加熱した状態で、水素と
一酸化炭素の高圧混合ガス（圧力；２．０ＭＰａ、
Ｈ2：ＣＯ＝２：１）を５０ｃｍ3／分の流速で流通させ
ることにより前記反応管の出口から水素化生成物を製造
した。Next, the obtained powdery catalyst was filled in a cylindrical high-pressure stainless steel reaction tube in the same manner as in Example 1, and the reaction tube was heated to 250 ° C. by a heater arranged outside, for example. In a heated state, a high-pressure mixed gas of hydrogen and carbon monoxide (pressure: 2.0 MPa,
(H 2 : CO = 2: 1) was passed at a flow rate of 50 cm 3 / min to produce a hydrogenated product from the outlet of the reaction tube.
【００４７】実施例４で得られた水素化生成物の混合ガ
ス中の一酸化炭素（ＣＯ）に対する転化率、水素化生成
物の成分分析を実施例１と同様な方法により行なった。The conversion of the hydrogenated product obtained in Example 4 to carbon monoxide (CO) in the mixed gas and the component analysis of the hydrogenated product were analyzed in the same manner as in Example 1.
【００４８】その結果、ＣＯ転化率は１５％、Ｃ5〜Ｃ9
のガソリン燃料油成分およびＣ10〜Ｃ20のディーゼル燃
料油成分の選択率はそれぞれ１６％，３７％であった。As a result, the CO conversion was 15%, and C 5 -C 9
The selectivity of the gasoline fuel oil component and the selectivity of the C 10 -C 20 diesel fuel oil component were 16% and 37%, respectively.
【００４９】なお、ＴＩＥ法に代えてＩＭＰ法によりル
テニウムをシリカ多孔質体に担持した触媒を用いた場合
でも、実施例４と同程度のＣ5〜Ｃ9のガソリン燃料油成
分およびＣ10〜Ｃ20のディーゼル燃料油成分の選択率が
得られた。Even when a catalyst in which ruthenium is supported on a porous silica material by the IMP method is used instead of the TIE method, a gasoline fuel oil component of C 5 to C 9 and C 10 to C selectivity of diesel fuel oil component to C 20 were obtained.
【００５０】したがって、実施例１〜４により製造され
た水素化生成物は簡単な分離操作によりガソリンやディ
ーゼルエンジンの燃料として有効に利用することができ
る。Therefore, the hydrogenated products produced in Examples 1 to 4 can be effectively used as gasoline or diesel engine fuel by a simple separation operation.
【００５１】[0051]
【発明の効果】以上詳述したように本発明によれば、水
素と一酸化炭素の混合ガスから目的とする成分（例えば
ガソリン燃料油成分またはディーゼル燃料油成分）を高
い選択率で含む水素化生成物を製造するのに適した一酸
化炭素の水素化反応触媒を提供することができる。As described above in detail, according to the present invention, hydrogenation containing a target component (for example, gasoline fuel oil component or diesel fuel oil component) at a high selectivity from a mixed gas of hydrogen and carbon monoxide. It is possible to provide a catalyst for hydrogenating carbon monoxide suitable for producing a product.
【００５２】また、本発明によれば水素と一酸化炭素の
混合ガスから目的とする成分（例えばガソリン燃料油成
分またはディーゼル燃料油成分）が高い選択率で含み、
簡単な分離操作によりガソリンやディーゼルエンジンの
燃料として利用できる水素化生成物の製造方法を提供す
ることができる。According to the present invention, a target component (for example, a gasoline fuel oil component or a diesel fuel oil component) is contained at a high selectivity from a mixed gas of hydrogen and carbon monoxide.
By a simple separation operation, it is possible to provide a method for producing a hydrogenated product that can be used as a fuel for gasoline and diesel engines.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ１０Ｇ 2/00 Ｃ１０Ｌ 1/02 Ｃ１０Ｌ 1/02 1/06 1/06 1/08 1/08 Ｂ０１Ｊ 23/74 ３１１Ｍ Ｆターム(参考） 4G069 AA03 AA08 BA02A BA02B BC66A BC67A BC67B BC70A BC70B BC71A BC75A CC22 CC31 DA05 EA01Y EB17X EB17Y EC13X EC13Y EC14X EC14Y EC15X FA02 FC08 4H013 BA03 4H029 CA00 DA00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C10G 2/00 C10L 1/02 C10L 1/02 1/06 1/06 1/08 1/08 B01J 23 / 74 311M F term (reference) 4G069 AA03 AA08 BA02A BA02B BC66A BC67A BC67B BC70A BC70B BC71A BC75A CC22 CC31 DA05 EA01Y EB17X EB17Y EC13X EC13Y EC14X EC14Y EC15X FA02 FC08 4H013 BA03 4H029 CA0300
Claims (8)
の微細孔を有する多孔体に遷移金属を担持したことを特
徴とする一酸化炭素の水素化反応触媒。(1) 90% or more of all pores have a diameter of 1 to 50 nm.
A hydrogenation catalyst for carbon monoxide, wherein a transition metal is supported on a porous body having fine pores.
とを特徴とする請求項１記載の一酸化炭素の水素化反応
触媒。2. The catalyst according to claim 1, wherein the porous body is based on silica.
孔が全細孔の９０％以上を占めることを特徴とする請求
項１記載の一酸化炭素の水素化反応触媒。3. The catalyst for hydrogenating carbon monoxide according to claim 1, wherein the porous body has micropores having a diameter of 1 to 10 nm occupying 90% or more of all the pores.
る場合、前記多孔体に５〜４０重量％の範囲で担持され
ることを特徴とする請求項１記載の一酸化炭素の水素化
反応触媒。4. The catalyst for hydrogenating carbon monoxide according to claim 1, wherein when the transition metal is cobalt or iron, the transition metal is supported on the porous body in a range of 5 to 40% by weight. .
または白金から選ばれる貴金属である場合、前記多孔体
に１〜１５重量％の範囲で担持されることを特徴とする
請求項１記載の一酸化炭素の水素化反応触媒。5. The monooxide according to claim 1, wherein when the transition metal is a noble metal selected from ruthenium, rhodium or platinum, the transition metal is supported on the porous body in a range of 1 to 15% by weight. Catalyst for hydrogenation of carbon.
界面活性剤（テンプレート）が残留する多孔体を遷移金
属化合物の水溶液に添加、混合して遷移金属イオンとテ
ンプレートイオンとを交換し、乾燥した後、焼成して前
記テンプレートを燃焼、除去することによりなされるこ
とを特徴とする請求項１ないし５いずれか記載の一酸化
炭素の水素化反応触媒。6. The supporting of the transition metal on the porous body,
By adding and mixing the porous body in which the surfactant (template) remains to an aqueous solution of the transition metal compound, exchanging the transition metal ion with the template ion, drying, firing and burning and removing the template. The catalyst for hydrogenating carbon monoxide according to any one of claims 1 to 5, wherein the catalyst is produced.
の微細孔を有する多孔体に遷移金属を担持した触媒の存
在下、一酸化炭素と水素を含む混合ガスを２００〜４０
０℃の温度、０．１〜１０ＭＰａの圧力の下にて反応さ
せることを特徴とする水素化生成物の製造方法。7. 90% or more of all pores have a diameter of 1 to 50 nm.
A mixed gas containing carbon monoxide and hydrogen is supplied in the presence of a catalyst in which a transition metal is supported on a porous body having fine pores of 200 to 40%.
A method for producing a hydrogenated product, wherein the reaction is carried out at a temperature of 0 ° C. under a pressure of 0.1 to 10 MPa.
よびディーゼル燃料油を含むことを特徴とする請求項７
記載の水素化生成物の製造方法。8. The hydrogenation product mainly comprises gasoline fuel oil and diesel fuel oil.
A process for producing the hydrogenation product described.
Priority Applications (2)
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|---|---|---|---|
| JP2000064874A JP3407031B2 (en) | 2000-03-09 | 2000-03-09 | Catalyst for hydrogenation reaction of carbon monoxide and method for producing hydrogenation product |
| US09/657,905 US6410477B1 (en) | 2000-03-09 | 2000-09-08 | Hydrogenation catalyst of carbon monoxide and method of manufacturing hydrogenation product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000064874A JP3407031B2 (en) | 2000-03-09 | 2000-03-09 | Catalyst for hydrogenation reaction of carbon monoxide and method for producing hydrogenation product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001246256A true JP2001246256A (en) | 2001-09-11 |
| JP3407031B2 JP3407031B2 (en) | 2003-05-19 |
Family
ID=18584496
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| US (1) | US6410477B1 (en) |
| JP (1) | JP3407031B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004352757A (en) * | 2003-05-27 | 2004-12-16 | Rikogaku Shinkokai | Ion-conducting polymer composition and filler for ion-conducting polymer |
| JP2006515584A (en) * | 2002-12-06 | 2006-06-01 | エービービー ルマス グローバル インコーポレイテッド | Mesoporous materials with active metals |
| JP2008101059A (en) * | 2006-10-17 | 2008-05-01 | Nippon Oil Corp | Isomerization method of paraffin |
| JP2008526474A (en) * | 2004-12-31 | 2008-07-24 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Reactor for solid / liquid / gas reaction |
| JP2014147868A (en) * | 2013-01-31 | 2014-08-21 | Kubota Corp | Method for producing fuel synthesis catalyst, fuel synthesis catalyst, and method for producing hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7201963B2 (en) * | 2002-01-15 | 2007-04-10 | Gentex Corporation | Pre-processed workpiece having a surface deposition of absorber dye rendering the workpiece weld-enabled |
| US7488462B2 (en) * | 2005-04-26 | 2009-02-10 | The Ohio State University | Multi-stage catalyst systems and uses thereof |
| US8119558B2 (en) * | 2008-03-14 | 2012-02-21 | Süd-Chemie Inc. | Ultra high temperature shift catalyst with low methanation |
| US9358526B2 (en) | 2013-11-19 | 2016-06-07 | Emerging Fuels Technology, Inc. | Optimized fischer-tropsch catalyst |
| US9180436B1 (en) | 2013-11-19 | 2015-11-10 | Emerging Fuels Technology, Inc. | Optimized fischer-tropsch catalyst |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2505205B1 (en) * | 1981-05-05 | 1986-05-23 | Inst Francais Du Petrole | NOVEL CATALYSTS OF NOBLE METALS OF GROUP VIII SUPPORTED AT HIGH DISPERSION AND HIGH ACTIVITY THEIR MANUFACTURE AND THEIR USE IN PARTICULAR IN HYDROGENATION REACTIONS |
| US4752622A (en) * | 1984-07-30 | 1988-06-21 | The Dow Chemical Company | Process for producing alcohols from synthesis gas |
| JPS61111140A (en) * | 1984-11-06 | 1986-05-29 | Toyota Central Res & Dev Lab Inc | Catalyst for synthesizing hydrocarbon |
| DE3917890A1 (en) * | 1989-06-01 | 1990-12-06 | Steinbach Friedrich | SUPPORTED CATALYSTS FOR THE REMOVAL OF NITROGEN OXIDE, CARBON MONOXIDE AND ORGANIC COMPOUNDS FROM EXHAUST GAS |
| US5506273A (en) * | 1991-12-06 | 1996-04-09 | Agency Of Industrial Science And Technology | Catalyst for hydrogenation and method for hydrogenation therewith |
| DE4319909C2 (en) * | 1993-06-16 | 1996-11-07 | Solvay Deutschland | Airgel supported catalyst comprising palladium, platinum, nickel, cobalt and / or copper, process for its production and use of a palladium airgel supported catalyst |
| US5648312A (en) * | 1994-12-29 | 1997-07-15 | Intevep, S.A. | Hydrogenation catalyst with improved attrition resistance and heat dissipation |
| US5895770A (en) * | 1995-02-28 | 1999-04-20 | Pq Corporation | Olefin polymerization catalysts with specific silica supports |
| DE19636768A1 (en) * | 1996-09-10 | 1998-03-12 | Basf Ag | Catalysts suitable for the production of aliphatic alpha, omega-aminonitriles by partial hydrogenation of aliphatic dinitriles |
-
2000
- 2000-03-09 JP JP2000064874A patent/JP3407031B2/en not_active Expired - Lifetime
- 2000-09-08 US US09/657,905 patent/US6410477B1/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006515584A (en) * | 2002-12-06 | 2006-06-01 | エービービー ルマス グローバル インコーポレイテッド | Mesoporous materials with active metals |
| JP2004352757A (en) * | 2003-05-27 | 2004-12-16 | Rikogaku Shinkokai | Ion-conducting polymer composition and filler for ion-conducting polymer |
| JP2008526474A (en) * | 2004-12-31 | 2008-07-24 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Reactor for solid / liquid / gas reaction |
| JP2008101059A (en) * | 2006-10-17 | 2008-05-01 | Nippon Oil Corp | Isomerization method of paraffin |
| JP2014147868A (en) * | 2013-01-31 | 2014-08-21 | Kubota Corp | Method for producing fuel synthesis catalyst, fuel synthesis catalyst, and method for producing hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3407031B2 (en) | 2003-05-19 |
| US6410477B1 (en) | 2002-06-25 |
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